JP2783671B2 - Toner, image forming apparatus, apparatus unit, and facsimile apparatus - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image in an image forming method such as electrophotography, and particularly relates to a heat fixing performance,
The present invention relates to a toner having improved offset resistance and electrostatic charge image development performance. Further, the present invention relates to an image forming apparatus, an apparatus unit, and a facsimile apparatus having a specific toner.

(Background technology)

Conventionally, many electrophotographic methods are known as described in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748.
Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is developed using a developer containing a toner. After a toner image is transferred to such a transfer material, the toner image is fixed by heat, pressure, heat and pressure or solvent vapor to obtain a copy, and the toner remaining on the photoreceptor without being transferred is subjected to various methods. It is cleaned and the above steps are repeated.

In recent years, such a copying apparatus has been used not only as a copying machine for office work for copying an original manuscript, but also as a digital printer as a computer output and a facsimile output, or for copying high-resolution images such as graphic designs. It is starting to be used.

Therefore, high reliability has been strictly pursued,
Along with this, the performance required of the toner has become higher, and if the performance of the toner cannot be improved, an excellent machine cannot be established.

By the way, one of the important performances required for toner in digital printers and copying of high-definition images is the fixing performance of fine lines.

Various methods and devices have been developed for the fixing step, but the most common method at present is a pressure heating method using a heat roller.

The pressure heating method using a heating roller performs fixing by allowing the toner image surface of a sheet to be fixed to pass through the surface of a heat roller having a surface formed of a material having releasability with respect to toner while contacting the surface under pressure. . In this method, since the surface of the heat roller and the toner image of the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image to the sheet to be fixed is extremely good, and the fixing can be performed quickly. Very effective in high-speed electrophotographic copying machines.
However, in the above-mentioned method, since the surface of the heat roller and the toner image come into contact with each other under pressure in a molten state, a part of the toner image adheres to and transfers to the surface of the heat roller. An offset phenomenon may occur, and the sheet to be fixed may be stained. Preventing toner from adhering to the surface of the heat roller is one of the essential conditions of the heat roller fixing system.

On the other hand, in the latent image portion of the fine image, the lines of electric force are concentrated at the boundary between the exposed portion and the non-exposed portion, and the surface potential of the photoconductor apparently increases. Especially in digital printers,
Since the latent image is composed of ON-OFF binary basic pixels, the concentration of lines of electric force at the boundary between the exposed part and the non-exposed part is large. The toner amount per unit area to be developed is larger than the toner amount on a normal analog image. Therefore, in the fixing of such an image, at present, a toner having a better fixing property and an offset property is required.

When used as a printer, the copy amount is 3 to 5 times that of a copier of the same level, and at the same time, high durability of development and high image stability are required.

As technology related to improvement of toner binder resin,
For example, Japanese Patent Publication No. 51-23354 proposes a toner using a crosslinked polymer as a binder resin. A toner using a crosslinked polymer is effective in improving the offset resistance and the anti-sticking property. However, when the degree of cross-linking is increased, the fixing point is increased, and the fixing temperature is sufficiently low and the offset resistance is lowered. In addition, it is difficult to obtain a toner having good smearing resistance and sufficient fixing characteristics. Generally, in order to improve the fixing property, the binder resin must have a low molecular weight to lower the softening point, which is inconsistent with the treatment for improving the offset resistance. Further, when the glass transition point of the resin is lowered in order to lower the softening point, an undesired phenomenon that the toner during storage blocks will occur.

Further, with respect to a toner blended with a low molecular weight polymer and a crosslinked polymer, for example, JP-A-58-86558 proposes a toner containing a low molecular weight polymer and an infusible high molecular weight polymer as main resin components. I have. According to this method, the fixability tends to be improved, but the weight average molecular weight / number average molecular weight (Mw / Mn) of the low molecular weight polymer is as small as 3.5 or less, and the content of the insoluble high molecular weight polymer is low. Amount is 40-90wt
%, It is difficult to satisfy both the fixing property and the offset resistance with high performance. Actually, it is extremely difficult to produce a toner that sufficiently satisfies the fixing property and the offset resistance unless it is for a fixing device having a liquid supply device for offset prevention.

JP-A-60-166958 discloses a number average molecular weight (Mn) of 500
A toner comprising a resin component obtained by polymerization in the presence of low molecular weight poly-α-methylstyrene having a molecular weight of 1,500 has been proposed.

In particular, in this publication, the number average molecular weight (Mn) is 9,000 to 30,000
Although the range of 0 is preferable, if Mn is increased to further improve the offset resistance, the fixing property becomes a practical problem. Therefore, it is difficult to satisfy the offset resistance with high performance.

Japanese Patent Application Laid-Open No. 56-16144 discloses that in a molecular weight distribution by GPC, a binder resin component having at least one maximum value is contained in each region of a molecular weight of 10 ³ to 8 × 10 ⁴ and a molecular weight of 10 ⁵ to 2 × 10 ^6. Toner has been proposed. In this case, the pulverizability, offset resistance, fixing property, filming and fusing to the photoreceptor, and image quality are excellent, but further improvement in the offset resistance and fixing property of the toner is demanded.

On the other hand, in order to satisfy the physical properties required for the toner, a method in which a polymer having a carboxylic acid is reacted with a metal compound in a binder resin to perform crosslinking (JP-A-57-1782)
No. 49, JP-A-57-178250), a binder having a vinyl resin monomer and a more specific half-ester compound as essential constitutional units and a polyvalent metal compound are reacted and crosslinked via a metal. (Japanese Patent Application Laid-Open No. 61-110155,
-110156) has been proposed.

Further, JP-A-63-214760, JP-A-63-217362
JP-A-63-217363 and JP-A-63-217364 have a molecular weight distribution divided into two groups, low molecular weight and high molecular weight, and a carboxylic acid group contained on the low molecular weight side. It is disclosed that a polyvalent metal ion is reacted and cross-linked (a dispersion of a metal compound is added to a solution obtained by solution polymerization and heated to react). In either case, the reaction between the binder resin and the metal compound or the dispersion of the metal compound in the binder resin is not sufficient, so that the material properties (especially fixing property and offset resistance) required of the toner are satisfied. Has not been reached. Further, since it is necessary to mix a large amount of the metal compound with the binder resin, the compounded metal compound exhibits a catalytic action on the binder resin depending on conditions, and the binder resin is easily gelled. As a result, it is difficult to determine the manufacturing conditions for obtaining the desired toner by blending the metal compound. Even if the manufacturing conditions can be determined, there is a problem that reproducibility is hardly obtained.

Even if the binder resin contains a carboxylic acid group that reacts with the metal compound, if the carboxylic acid group is in an anhydrated (ie, ring-closed) state, the crosslinking reactivity with the metal compound is weak. As a result, the cross-linking strength is not sufficient and the offset resistance and the fixing property are not satisfied.

Further, JP-A-63-216063 proposes to combine ionic crosslinking by a metal in a binder resin with an offset inhibitor, and JP-A-62-280757 proposes to combine an acid anhydride group in a binder with an acid anhydride group. It has been proposed to form a polar functional group by reaction with a cationic component to improve the chargeability of the toner. However, even such a method does not satisfy all the physical properties required for the toner, such as offset resistance, fixing property, and developing property.

JP-A-59-214860 proposes to improve the fixing property and the offset resistance by using a toner obtained from a resin having a viscoelastic property in a specific range.However, the offset resistance has a certain effect. As shown, the elastic modulus and the viscosity were too high and their frequency dependence was large, so that the compatibility between the low-temperature fixability and the offset resistance was unsatisfactory.

JP-A-63-223662 discloses that offset resistance is achieved by using a binder resin containing 10 to 60 parts by weight of a THF-insoluble component and having two peaks in the molecular weight distribution of the THF-soluble component. However, from high-speed machines to low-speed machines, further improvement in low-temperature fixing property, blocking resistance, and offset resistance is desired.

As described above, a toner that can satisfy the fixing performance and the offset resistance, and particularly, a toner that can favorably develop a digital latent image is desired.

[Object of the invention]

An object of the present invention is to provide a toner that solves the above-mentioned problems.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner which is excellent in both fixing property and offset property, has good image reproducibility, and has no reversal fog.

A further object of the present invention is to provide a toner which does not cause image deterioration even when used for a long time.

Another object of the present invention is to provide a toner which can be fixed at a low temperature and has excellent blocking resistance, and can be used particularly well in a high-temperature atmosphere in a small-sized copying machine.

Still another object of the present invention is to provide a toner which has excellent offset resistance and which has good production efficiency.

It is a further object of the present invention to provide a toner having a high image density and excellent fine line reproducibility and gradation.

A further object of the present invention is to provide a toner capable of maintaining a stable high image density without depending on the environment.

An object of the present invention is to provide an image forming apparatus having a specific toner.

An object of the present invention is to provide an apparatus unit having a specific toner.

An object of the present invention relates to a facsimile apparatus having a specific toner.

[Summary of the Invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner containing at least a binder resin and a metal salt or a metal complex with a frequency of 1
× 10 ^-2 ~1 (Hz) dynamic elastic modulus of the toner G at 120 to 200 ° C. as measured in the range of _{'120 to 200} ^{is, 2 × 10 3 [dyne /} cm 2]
The toner has a loss elastic modulus G ″ of ₁₂₀ to 200 ° C. at a temperature of 120 to 200 ° C. in a range from the above to less than 5 × 10 ⁵ [dyne / cm ² ] and a frequency of 1 × 10 ⁻² to 1 (Hz). Is 2 × 10 ³ [dyne / cm
² ] to less than 5 × 10 ⁵ [dyne / cm ² ].
_{0 200 = a · logf + logb} [ wherein 'formula logG by the least squares method the relationship between the ₂₀₀ and the frequency f' dynamic modulus G ° C., G 'represents a dynamic modulus at 200 ° C. of the toner, f Indicates a frequency, and a and b indicate constants.] When approximation by a straight line represented by
A positive number less than 25 and 200 at a frequency of 1 [Hz]
Provide a toner that dynamic modulus at ℃ (G _'200) and dynamic elastic modulus of 120 ° C. (G' ratio of _{200) (G '200 / G} ' 120) is equal to or less than 0.25 Is to do.

Further, an object of the present invention is to store an electrostatic latent image carrier, a developer carrier for carrying a toner for developing the electrostatic latent image and transporting the toner to a development area, and the toner. In an image forming apparatus having at least a developing device having a developer accommodating chamber, the toner contains at least a binder resin and a metal salt or a metal complex, and has a frequency of 1 × 10 ⁻² to 1 (Hz). Measured in the range of 120
Dynamic modulus G _{'120 to 200 [toner} at to 200 DEG ° C. is, 2 × 1
0 ³ [dyne / cm ² ] or more and less than 5 × 10 ⁵ [dyne / cm ² ], measured at a frequency of 1 × 10 ⁻² to 1 (Hz)
120 to 200 loss modulus G _{"of 120 to 200} of the toner at ℃ is 2
It is in the range of not less than × 10 ³ [dyne / cm ² ] to less than 5 × 10 ⁵ [dyne / cm ² ], and the relationship between the dynamic elastic modulus G ′ _{200 at} 200 ° C. and the frequency f is calculated by the following method using the least square method. logG ′ ₂₀₀ = a · logf + logb [where G ′ represents the dynamic elastic modulus of the toner at 200 ° C., f represents the frequency, and a and b represent constants] The value of the constant a in the formula is 0.
A positive number less than 25 and 200 at a frequency of 1 [Hz]
Dynamic modulus at ℃ (G _'200) and dynamic elastic modulus of ₁₂₀ ℃ (G' 120) the ratio between _{(G '200 / G' 120} ) is an image forming apparatus and less than 0.25 Is to provide.

Still another object of the present invention is to provide an electrostatic latent image carrier and a developing device for developing the electrostatic latent image. The developing device has a developer accommodating chamber accommodating toner, and a toner accommodating chamber. And a developer carrier for conveying the toner to the developing area. The developing device is integrally supported with the electrostatic latent image carrier to form a unit, and is detachably attached to the apparatus main body. In a device unit forming a single unit, the toner contains at least a binder resin and a metal salt or a metal complex, and has a frequency of 1 × 10 ^−2.
To 1 dynamic modulus G _{'120 to 200 [toner} at 120 to 200 [° C. were measured in the range (Hz) ^{is, 2 × 10 3 [dyne /} cm 2] or more to ^{5 × 10 5 [dyne / cm} 2 ], And the frequency is 1 × 1
0 ^-2 ~1 (Hz) Loss modulus G _{"120 to 200 [toner} at 120 to 200 [° C. as measured in the range ^{of, 2 × 10 3 [dyne /} cm 2] or more to ⁵ × 10 5 [dyne / cm ² ], and the relationship between the dynamic elastic modulus G ′ ₂₀₀ and the frequency f at 200 ° C. is calculated by the least square method using the following equation: log G ′ ₂₀₀ = a · logf + logb [where G ′ is the toner 200 ° C.] , F represents frequency, and a and b represent constants] When approximated by a straight line represented by the following expression, the value of the constant a in the equation is 0.
A positive number less than 25 and 200 at a frequency of 1 [Hz]
An apparatus unit characterized in that the ratio (G ′ ₂₀₀ / G ′ ₁₂₀ ) of the dynamic elastic modulus at 120 ° C. (G ′ ₂₀₀ ) to the dynamic elastic modulus at 120 ° C. (G ′ ₁₂₀ ) is less than 0.25. To provide.

Further, an object of the present invention is to provide a facsimile apparatus having at least a receiving unit for receiving image information from an electrophotographic apparatus and a remote terminal, wherein the electrophotographic apparatus develops an electrostatic latent image carrier and an electrostatic latent image. A developing device, the developing device having a developer accommodating chamber for accommodating the toner, and a developer carrying member for carrying the toner and transporting the toner to the developing area. Contains at least a binder resin and a metal salt or a metal complex, and is measured at a frequency of 1 × 10 ⁻² to 1 (Hz).
Dynamic modulus G _{'120 to 200 [toner} at 0 to 200 ° C., 2 ×
It was in the range of 10 ³ [dyne / cm ² ] or more to less than 5 × 10 ⁵ [dyne / cm ² ], and was measured in the frequency range of 1 × 10 ^-2 to 1 (Hz).
120 to 200 loss modulus G _{"of 120 to 200} of the toner at ℃ is 2
It is in the range of not less than × 10 ³ [dyne / cm ² ] to less than 5 × 10 ⁵ [dyne / cm ² ], and the relationship between the dynamic elastic modulus G ′ _{200 at} 200 ° C. and the frequency f is calculated by the following method using the least square method. logG ′ ₂₀₀ = a · logf + logb [where G ′ represents the dynamic elastic modulus of the toner at 200 ° C., f represents the frequency, and a and b represent constants] The value of the constant a in the formula is 0.
A positive number less than 25 and 200 at a frequency of 1 [Hz]
The ° C. facsimile device dynamic elastic modulus (G _'200) and dynamic elastic modulus of ₁₂₀ ℃ (G' 120) the ratio between _{(G '200 / G' 120} ) is equal to or less than 0.25 in To provide.

[Specific description of the invention]

In the present invention, the value of a in the formula when approximated by a straight line represented 'the relationship between ₂₀₀ and f formula logG by the least square method' dynamic modulus G 200 ° C. of the toner at ₂₀₀ = a · logf + logb Is a positive number less than or equal to 0.25.

The value of a corresponds to the slope of the straight line represented by the above equation on the log-log graph, and indicates that the value of G ′ changes more with a change in frequency as | a | increases. Since a change in frequency can be converted into a change in temperature according to the time-temperature conversion rule, it can be rephrased that the larger the value of | a |, the larger the value of G 'changes with a change in temperature.

The thermal properties of the toner are deeply involved in fixing. As a property necessary for the fixing property, it is necessary that the toner is not softened more than necessary so that the toner is softened as much as possible when passing through a heat roller under pressure and a high-temperature offset does not occur. Further, it is necessary that the elastic modulus of the toner does not significantly change due to the temperature change in view of the stability of the fixing and the offset resistance. In the toner of the present invention, the frequency f = 1
× 10 ^-2 ~1 (Hz) dynamic modulus at 120 ° C. to 200 DEG ° C. were measured in the range of G '(or G1) _{120 to 200 [and} loss modulus G "
(Or G2) ₁₂₀ to ₂₀₀ is 2 × 10 ^{3 to} less than 5 × 10 ⁵ (dyne / c
By being within the range of m ² ), good fixing properties are exhibited without generating high-temperature offset during fixing. G '
The relationship between ₂₀₀ and f is shown. When the value of a in the formula is a positive number of 0.25 or less, the change in the elastic modulus due to the change in temperature of 200 ° C. or more is gradual, so that the temperature around the roller at the time of fixing has a certain amplitude. However, the fixing property and the offset resistance are stable.

In the toner of the present invention, the dynamic elastic modulus and the loss elastic modulus at 200 ° C. do not substantially change with time, so that even if heat from the fixing roller is applied to the toner cleaned by the fixing cleaning member for a long time. There is no problem that the collected toner or developer flows out of the cleaning member.

When a toner having G 'of ₁₂₀ to ₂₀₀ lower than 2 × 10 ³ [dyne / cm ² ] is used, the offset resistance is insufficient and G'
_{When a} toner in which ₁₂₀ to ₂₀₀ exceeds 5 × 10 ⁵ [dyne / cm ² ] is used, the low-temperature fixability becomes insufficient.

The viscoelasticity of the toner of the present invention is measured using a rheometer IR-200 manufactured by Iwamoto Seisakusho using a parallel plate having a diameter of 3 cm.

The toner of the present invention has a dynamic elastic modulus measured in the frequency range of 1 × 10 ^-2 to 1 (Hz) at a value measured at 120 ° C. (G ′ ₁₂₀ ) and a value measured at 200 ° C. (G ′ ₂₀₀ ). At the same frequency (G ' ₂₀₀ / G' ₁₂₀ is less than 0.25 (0.
05 or more is preferable), and by simultaneously satisfying the above-mentioned viscoelastic properties, sufficient low-temperature fixability, offset resistance, and blocking resistance can be achieved.

Although there are various means for the toner of the present invention to exhibit the viscoelastic property, it is preferable that the binder resin in the toner of the present invention is as described below.

The binder resin in the toner of the present invention has a molecular weight distribution of 2,000 to 15,
Having at least one peak in a region of less than 000, and having at least a peak or shoulder in a region of a molecular weight of 15,000 to 100,000, and including a carboxyl group-containing monomer or a carboxylic acid derivative monomer as a component, Of the resin
The ratio (A / B) between the JIS acid value (A) measured by a method according to JISK-0070 and the total acid value (B) measured after hydrolyzing the acid anhydride of the resin is 0.75 to 0.99. Preferably, there is.

The THF-insoluble content of the resin is preferably 5 to 70 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of the resin.

When the binder resin is dissolved in a solvent such as THF, insolubles and solubles can be separated, and the molecular weight distribution of the solubles can be measured by GPC. Paying attention to the positions of the peaks of the molecular weight distribution of the THF-insoluble component and the THF-soluble component, a system having no or little THF-insoluble component is very disadvantageous in pulverizability at the time of producing pulverized toner. In order to improve the pulverizability, the direction in which the molecular weight distribution peak of the THF-soluble component is simply shifted to the lower molecular weight position will deteriorate the offset resistance and satisfy both the offset resistance and the pulverizability. Is difficult.

From this study, it is very effective to include a specific amount of THF-insoluble components not only for offset resistance but also for improving pulverizability, as generally considered.

Furthermore, from the consideration of the molecular weight distribution of the THF-soluble component and the property of whether the fixing temperature is high or low (hereinafter simply referred to as fixing property), the offset resistance, the crushing property, and the blocking resistance, the basics of the binder resin are In addition, THF-insoluble components mainly affect the offset resistance, the blocking property, and the pulverizability of the cooled kneaded material during toner production. The components soluble in THF having a molecular weight of less than 15,000 mainly affect the pulverizability of the kneaded and cooled product during toner production, the blocking ability of the toner, the fusing property to the photoconductor, the filming property, and the fusing to the inner wall of the pulverizing device. give. Further, the components having a molecular weight of 15,000 or more in the THF-soluble component mainly affect the offset resistance and the fixing property.

To specifically explain the present invention, the binder resin used in the toner of the present invention preferably has a THF-insoluble content (gel component) of 5 to 70% by weight (based on the binder resin), more preferably 20 to 60% by weight, GPC of other THF soluble components
In the chromatogram, the molecular weight has at least one peak in the region of 2,000 to less than 15,000, more preferably 3,000 to 12,000, and the molecular weight is 15,000 to 100,000,
More preferably, it has at least one peak or shoulder in the region of 20,000 to 70,000. More preferably, the molecular weight is 2,000
A peak in the region of 0 to less than 15,000 and a molecular weight of 15,000 to 1
The peak or shoulder gap in the region of 00,000 is the molecular weight
The difference should be 5,000 or more (preferably 10,000 or more).

When the THF-insoluble content in the resin composition exceeds 70%, the fixing temperature of the toner is increased, and the dispersion of the additive in the binder resin tends to be poor. Further, the components of the highly crosslinked region are liable to be cut off during the kneading of the resin, which tends to hinder the design of the toner. If the THF-insoluble component is less than 5%,
If the offset and winding around the roller are apt to occur, and if the THF-insoluble component is less than 5% and the high molecular weight region is large, the pulverizability tends to be remarkably deteriorated. In the region where the molecular weight of the THF solvent-soluble component is 2,000 to less than 15,000, there is no peak value, and when the peak value is 15,000 or more, the fixing temperature of the prepared toner increases, the fixing temperature range becomes narrow, and the pulverizability deteriorates. There is a tendency for production efficiency to decrease. If the peak molecular weight is less than 2,000, the produced toner has extremely poor offset resistance, which may cause a problem in blocking. If the molecular weight of the other peak or shoulder is not in the range of 15,000 to 100,000 and the value exceeds 100,000, the dispersibility of the additive is poor, the fixing temperature is significantly increased, and the grindability tends to be significantly deteriorated. If the molecular weight at the peak or shoulder is less than 15,000, the produced toner has poor offset resistance, which may cause a problem in blocking.

Furthermore, in order to fully satisfy the offset resistance,
Molecular weight based on the ratio of THF insolubles in the binder resin and THF solubles
In addition to increasing the proportion of components of 15,000 or more, it is preferable that a cross-linking reaction can occur between the metal compound and the carboxyl group, and those in which the carboxyl group can be dehydrated in the molecule are particularly preferable, especially when the metal compound is used. With high crosslinking reactivity.

This cross-linking reaction is accelerated by heat, and part of the carboxyl group is involved in the cross-linking reaction with the metal compound at the time of melt-kneading in producing a toner, and part of the carboxyl group is dehydrated.

Since most of the carboxyl groups in the binder resin are involved in these reactions, the charge using the binder resin having a carboxyl group, which is typical of toner with a reduced amount of charge due to moisture absorption under high temperature and high humidity There are no, but very few, problems with environmental characteristics related to sex. When the carboxyl group is dehydrated, there is a merit that a sufficient negative charging ability can be given to the binder itself and that the toner can have a good negative charging property.

Further, most of the carboxyl groups participate in the cross-linking, and the polarity of the binder resin is maintained even when the binder resin is further dehydrated, so that the affinity to paper is improved and the fixing property is further improved. Therefore, the Tg (glass transition point) of the binder resin can be increased, and the blocking resistance is also improved.

^{1 × 10 -2 [Hz] ~1} [Hz] Dynamic viscoelasticity G _{'120 to 200 [is} 2 × 10 ³ or more less than 5 × 10 ^5, measured at 120 ° C. to 200 DEG ° C. in the frequency range of the toner of the present invention In order to have the above value, the configuration of the binder resin is preferable.

Copolymers or copolymer compositions containing these monomer units having a carboxyl group are partially hydrolyzed at the time of suspension polymerization, as described later, to form a dicarboxylic acid group and a carboxylic acid. Groups and carboxylic anhydride groups.

These three kinds of acid components in the copolymer or the copolymer composition interact with each other via metal ions of a metal salt or a metal complex, which is another component of the present invention, to form various polymer complexes. It is considered to form

Therefore, the resin for toner of the present invention contains metal crosslinks (ionic crosslinks) by various polymer complexes having different bond strengths and strong crosslinks by a polymerizable crosslinker. By mixing various types of crosslinks having different viscoelastic properties, a toner exhibiting the above-mentioned specific viscoelastic properties can be obtained, which is excellent in blocking resistance, low temperature fixing and offset resistance.

Crosslinking of polymers or copolymers containing dicarboxylic acid on the low molecular weight side via metal ions can improve the blocking resistance of toner without increasing the Tg of the polymer or copolymer. Become. Since it is not necessary to raise Tg to improve blocking resistance,
The dynamic elastic modulus and the loss elastic modulus measured in the above are 5 × 10 ⁵ [dyne
Cm ² ] or less, and low-temperature fixing can be achieved.

When a polymer or copolymer having a high Tg is used and the blocking resistance is improved, the dynamic elastic modulus and the loss elastic modulus at 120 ° C. become 5 × 10 ⁵ [dyne · cm ² ] or more, It is difficult to achieve fixation.

Further, since the crosslinks having various bond strengths are present in the polymer or copolymer, the dynamic elastic modulus and the loss elastic modulus at 200 ° C. can be kept at 2 × 10 ³ [dyne · cm ² ] or more. Can,
The frequency dependence of the elastic modulus G ′ ₂₀₀ at 200 ° C. measured in the frequency range of 1 × 10 ⁻² to 1 [Hz] can be made extremely small.

As described above, since the toner of the present invention contains crosslinks having various bonding strengths in the binder, the dynamic elastic modulus and the loss elastic modulus at 200 ° C. do not substantially change with time. here,
"Substantially does not change with time" means that the rate of increase in dynamic elastic modulus and loss elastic modulus when held at 200 ° C. for 1 hour is 0.8 to 1.8 times, and more preferably 0.9 to 1.5 times. Therefore, the outflow of toner from the fixing cleaning member can be effectively prevented, and the problem of damaging the fixing roller does not occur.

When the increase rate of the dynamic elastic modulus and the loss elastic modulus is less than 0.5 times, the toner easily flows out of the fixing cleaning member, and when the increase rate is more than 1.8 times, the fixing roller is damaged when left at a high temperature for a long time. Cheap.

As described above, in the present invention, the content ratio of the carboxylic acid group, particularly the dicarboxylic acid group and its derivative in the vinyl resin for toner has a great influence on the viscoelasticity of the toner, and conforms to JIS K-0070 of the vinyl resin. Ratio (A / B) of the JIS acid value (A) measured by the above method and the total acid value (B) measured after hydrolyzing the acid anhydride group of the vinyl resin is 0.75 to 0.99.
Vinyl resin together with a metal salt or metal complex,
It is preferably obtained by melt-kneading.

If the A / B ratio is less than 0.75, the ratio of the acid anhydride becomes too large, the improvement in blocking resistance becomes insufficient, and it is difficult to obtain the viscoelastic properties required in the present invention.

When the A / B ratio exceeds 0.99, almost no acid anhydride groups are present, and the charging characteristics of the toner become unstable, which tends to cause a problem in image quality.

 The total acid value (B) is measured as follows.

2 g of the sample resin was dissolved in 30 ml of dioxane, and 10 ml of pyridine, 20 mg of dimethylaminopyridine, and 3.5 ml of water were added thereto.
And refluxed for 4 hours while stirring. After cooling, 1 /
The acid value obtained by neutralization titration with 10N KOH / THF solution using phenolphthalein as an indicator is defined as the total acid value (B). Preparation of a 1 / 10N KOH / THF combined solution is performed as follows. K
Dissolve 1.5 g of OH with about 3 ml of water, add 200 ml of THF and 30 ml of water
And stir. After standing, add a small amount of methanol if the solution has separated, or a small amount of water if the solution is cloudy, make a uniform transparent solution, and standardize with a 1 / 10N HCl standard solution.

The outline of the method for measuring the JIS acid value (A) according to JIS K-0070 is described below.

 The following reagents are used for acid value measurement.

Reagent (a) Solvent Ethyl ether-ethyl alcohol mixed liquid (1 + 1 or 2 + 1) or benzene-ethyl alcohol mixed liquid (1 + 1 or 2 + 1), and these solutions were prepared immediately before use using phenolphthalein as an indicator and N / 10 potassium hydroxide ethyl alcohol. Neutralize with solution.

(B) Phenolphthalein solution Dissolve 1 g of phenolphthalein in 100 ml of ethyl alcohol (95 v / v%).

(C) N / 10 potassium hydroxide-ethyl alcohol solution 7.0 g of potassium hydroxide is dissolved in as little water as possible, and ethyl alcohol (95 v / v%) is added to make 1; The standardization is performed according to JIS K8006 (basic matter on titration during content test of reagent).

 Next, the procedure of the method for measuring the acid value will be described.

Weigh the sample correctly, add 100 ml of solvent and a few drops of phenolphthalein solution as indicator and shake well until the sample is completely dissolved. In the case of a solid sample, dissolve by heating on a water bath. After cooling, the solution is titrated with an N / 10 solution of potassium hydroxide in ethyl alcohol, and the end point of neutralization is defined as the time when the indicator remains slightly red for 30 seconds.

 The acid value is calculated by the following equation.

Where A: acid value B: amount of N / 10 potassium hydroxide ethyl alcohol solution used (ml) f: factor of N / 10 potassium hydroxide ethyl alcohol S: sample (g) Insoluble matter in THF in the present invention Indicates the weight ratio of the polymer component (substantially crosslinked polymer) insoluble in the THF solvent in the resin composition in the toner, and is used as a parameter indicating the degree of crosslinking of the resin composition containing the crosslinking component. be able to. The THF-insoluble matter is defined by a value measured as follows.

0.5 to 1.0 g of the toner sample is weighed ( ₁ g of W), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kabushiki Kaisha), subjected to a Soxhlet extractor, extracted with 100 to 200 ml of TFH as a solvent for 6 hours, and extracted with the solvent. After evaporating the obtained soluble component, it is vacuum-dried at 100 ° C. for several hours, and the amount of the THF-soluble resin component is weighed (W ₂ g). The weight of a component other than the resin component such as a magnetic substance or a pigment in the toner is defined as (W ₃ g). The THF-insoluble content is obtained from the following formula.

In the present invention, the peak of the chromatogram by GPC (gel permeation chromatography) or the molecular weight of the shoulder is measured under the following conditions.

Stabilize the column in a heat chamber at 40 ° C, flow THF (tetrahydrofuran) as a solvent through the column at this temperature at a flow rate of 1 ml per minute, and set the sample concentration as
A THF sample solution of the resin adjusted to 0.05 to 0.6% by weight is 50 to 20%.
Measure by injecting 0μ. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 10 ² , 2.1 × 10 ³ ,
4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ ,
It is suitable to use 8.6 × 10 ⁵ , 2 × 10 ⁶ and 4.48 × 10 ⁶ , and to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

In order to accurately measure a molecular weight region of 10 ³ to 4 × 10 ^6, a plurality of commercially available polystyrene gel columns are preferably used in combination. For example, μ-styrage 150 manufactured by Waters
0, 10 ³ , 10 ⁴ 10 ⁵ combinations and Shodex K manufactured by Showa Denko
F-80M or a combination of KF-802, 803, 804, 805 or TSKgel G1000H, G2000H, G2500H, G300 manufactured by Toyo Soda
A combination of 0H, G4000H, G5000H, G6000H, G7000H, and GMH is preferred.

The weight% of the binder resin having a molecular weight of 10,000 or less according to the present invention cuts out the molecular weight of 10,000 or less in the chromatogram by GPC, calculates the weight ratio with the cutout having a molecular weight of 10,000 or more, and takes into account the weight% of the THF-insoluble component. The weight% with respect to the whole binder resin is calculated.

The polymerizable monomer containing a carboxylic acid group that can be used in the present invention includes the following. Α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid; α, β-unsaturated dicarboxylic acids such as maleic acid and fumaric acid or half esters thereof; n-butenyl succinic acid, n-butenyl adipic acid Alkenyl dicarboxylic acids or half esters thereof are mentioned.

Examples of the half-ester monomer of dicarboxylic acid that can be used in the present invention include, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate, monophenyl maleate, monomethyl fumarate, monomethyl fumarate Α, β-unsaturated dicarboxylic acid half esters such as monobutyl fumarate and monophenyl fumarate; monobutyl n-butenylsuccinate, monomethyl n-octenylsuccinate, monoethyl n-butenylmalonate,
Half-esters of alkenyl dicarboxylic acids such as monomethyl n-dodecenyl glutarate and monobutyl n-butenyl adipate; aromatic dicarboxylic acids such as monomethyl phthalate, monoethyl phthalate and monobutyl phthalate Half esters.

The above half ester of dicarboxylic acid is added in an amount of 1 to 30% by weight, preferably 3 to 20% by weight, based on all monomers constituting the binder resin.

The reason why the above-mentioned dicarboxylic acid half ester monomer is selected is that a suspension polymerization method is preferable as a method for producing a resin. This is because, in the suspension polymerization method, it is not appropriate to use an acid monomer having a high solubility in an aqueous suspension, and it is preferable to use an ester having a low solubility in an ester.

The comonomers other than the polymerizable monomer containing a carboxylic acid group for obtaining the binder resin of the present invention include the following.

For example, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p
-Phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, styrene derivatives such as pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene and pn-dodecylstyrene; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; butadiene Unsaturated polyenes; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate; Propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Α-methylene aliphatic monocarboxylates such as ethyl, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate; acrylic Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate,
Acrylic esters such as propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether Vinyl ethers such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide. These vinyl monomers are used alone or in combination of two or more.

Among these, a combination of monomers that results in a styrene-based copolymer and a styrene-acrylic copolymer is preferred.

As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used.

It is important that the binder resin used in the present invention is a copolymer crosslinked with a crosslinkable monomer as exemplified below in order to achieve the object of the present invention.

Aromatic divinyl compounds (for example, divinylbenzene,
Divinylnaphthalene); diacrylate compounds linked by an alkyl chain (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-
Butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); an alkyl chain containing an ether bond Tied diacrylate compounds (eg, diethylene glycol diacrylate, triethylene glycol diacrylate,
Tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); a chain containing an aromatic group and an ether bond (For example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) Enil)
Propane diacrylate and acrylates of the above compounds in which methacrylate is substituted); polyester-type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)). Examples of the multifunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and those obtained by replacing the acrylate of the above compound with methacrylate; Allyl cyanurate and triallyl trimellitate are exemplified.

These crosslinking agents are preferably used in an amount of 0.01 to 5 parts by weight (more preferably 0.03 to 3 parts by weight) based on 100 parts by weight of the other vinyl monomer components.

Among these crosslinkable monomers, aromatic divinyl compounds (particularly divinylbenze) are preferably used in toner resins in terms of fixing properties and offset resistance.
Examples include diacrylate compounds linked by a chain containing an aromatic group and an ether bond.

As a method for preparing a binder resin according to the present invention, a method for preparing two or more polymers or copolymers is basically preferable.

The THF insoluble content is small, and a low molecular weight polymer or copolymer soluble in the polymerizable monomer is dissolved in the polymerizable monomer,
In this method, a monomer is polymerized to obtain a resin composition. In this case, a resin composition in which the former and the latter polymers or copolymers are uniformly mixed is formed. The low molecular weight polymer or copolymer in the binder resin composition used in the present invention can be obtained by a polymerization method such as a bulk polymerization method and a solution polymerization method.

More preferably, a solution polymerization is carried out to produce a low molecular weight polymer or copolymer containing an acid anhydride group, and then the polymer or copolymer is dissolved in a polymerizable monomer to prepare a monomer composition, and then an aqueous system is prepared. It is preferred that the monomer composition is subjected to suspension polymerization in a medium to generate a dicarboxylic acid group. The low molecular weight polymer or copolymer obtained by the solution polymerization may be repolymerized together with a monomer giving a high molecular weight polymer or copolymer. Emulsion polymerization or suspension polymerization is also preferable as a polymerization method for obtaining a gel component in a crosslinked region until the polymer or copolymer becomes an insoluble component in a solvent.

As the reactive metal compound used in the present invention, those containing the following metal ions can be used. Monovalent metal ions include Na ⁺ , Li ⁺ , Cs ⁺ , Ag ⁺ , Hg ⁺ , and Cu ⁺ , and divalent metal ions include Ba ²⁺ , Mg ²⁺ , Ca ²⁺ , and Hg ²⁺ , Sn ²⁺ , Pb ²⁺ , Fe
²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ . The trivalent metal ions include Al ³⁺ , Sc ³⁺ , Fe ³⁺ , Ce ³⁺ , Ni ³⁺ , Cr ³⁺ , and Y ³⁺ . Among the compounds containing metal ions as described above, those which are more easily decomposed give better results. This is presumed to be due to the fact that the metal ion in the compound is easily bonded to the carboxyl group in the polymer or copolymer by thermal decomposition.

Among the reactive metal compounds, the organometallic compounds are excellent in compatibility and dispersibility with the polymer, and the crosslinking reaction proceeds uniformly in the polymer or copolymer, so that excellent results are obtained.

Among the reactive organometallic compounds as described above, those containing an organic compound which is particularly highly vaporizable and sublimable as a ligand and a counter ion are useful. Examples of the organic compound having the above-mentioned properties among organic compounds forming a coordination or counter ion with a metal ion include salicylic acid, salicylamide, salicylamine, salicylaldehyde, salicylosalicylic acid, and di-tert-butylsalicylic acid. Salicylic acid and its derivatives; β-diketones such as acetylacetone and propionacetone; and low-molecular carboxylate salts such as acetate and propionic acid.

In the toner of the present invention, a conventionally known charge control agent is used depending on the intended use. It is also a preferable embodiment of the present invention that the metal complex in the foreground also serves as the charge control agent.

For example, as the negative charge control agent, there is an azo-based metal complex represented by the following formula [I].

(Wherein M represents a coordination center metal, and Cr, Co,
Examples include metal elements such as Ni and Fe. Ar is an aryl group
And groups such as a phenyl group and a naphthyl group.
It may have a substituent. In this case, as a substituent,
Nitro group, halogen group, carboxyl group, anilide group
And a group such as an alkyl group having 1 to 18 carbon atoms and an alkoxy group
is there. X, X ', Y and Y' are -O-, -CO-, -NH
-, -NR- (R is an alkyl group having 1 to 4 carbon atoms).
K Is hydrogen, sodium, potassium, ammonium, fat
Indicates aliphatic ammonium. Next, specific examples of the complex will be shown.

The basic organic acid metal complex represented by the following formula [II] also gives a negative charge and can be used in the present invention.

[Wherein, M represents a coordination center metal, and Cr, C having a coordination number of 6
Metal elements such as o, Ni, Mn, and Fe are included. A is(Which may have a substituent such as an alkyl group), (X represents a hydrogen atom, a halogen atom, a nitro group)
And(R is a hydrogen atom, C₁~ C₁₈Alkyl or alkenyl of
Represents a group). Y Is hydrogen, sodium, potassium
Counter ions such as ammonium, ammonium and aliphatic ammonium
Is shown. Z is -O- orIs shown. These metal complexes may be used alone or in combination of two or more.
It is also possible to use them together.

The amount of the metal complex to be added to the toner is as follows:
0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 0 parts by weight.
Parts by weight, more preferably 1 to 5 parts by weight.

By reacting the metal complex at the time of melt-kneading with the binder resin, compared to the case of adding during the synthesis of the binder resin, rich in decomposition and reactivity, and excellent in compatibility with the binder or dispersibility in the binder, There is an advantage that stable charging properties can be obtained as a toner.

An additive (an internal additive or an external additive) may be added to the toner of the present invention as needed. As the colorant, conventionally known dyes and / or pigments can be used. Usually, the nonmagnetic colorant is used in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the binder resin. Other additives (external additives) include, for example, a lubricant such as zinc stearate; or an abrasive such as cerium oxide and silicon carbide; a fluidity-imparting agent such as colloidal silica and aluminum oxide; or an anti-caking agent; And a conductivity imparting agent such as tin oxide.

Wax-like substances such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, carnauba wax, sasol wax, paraffin wax for 0.5-5
The addition to the wt% toner is also one of the preferred embodiments of the present invention.

Further, the toner of the present invention may also serve as a colorant, but may contain a magnetic material. Examples of the magnetic material contained in the magnetic toner of the present invention include iron oxides such as magnetite, γ-iron oxide, ferrite, and iron-rich ferrite;
Metals such as iron, cobalt, nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth,
Cadmium, calcium, manganese, selenium, titanium,
Alloys with metals such as tungsten, vanadium and mixtures thereof.

The magnetic material is used in an amount of 20 to 140 parts by weight, preferably 30 to 120 parts by weight, based on 100 parts by weight of the binder resin.

Further, the magnetic material has a number average particle diameter of 0.1 to 1 μm, preferably 0.1 to 0.3 μm.

To prepare the toner for developing an electrostatic image of the present invention, a binder resin, a metal salt or a metal complex, a magnetic material as a colorant, a face amount or a dye, a charge control agent, if necessary, and other additives. After thoroughly mixing with a mixer such as a ball mill, melting, kneading and kneading using a hot kneader such as a heating roll, kneader or extruder to make the resins compatible with each other, the magnetic material and pigment Alternatively, the dye according to the present invention can be obtained by dispersing or dissolving the dye, and then pulverizing and classifying after cooling and solidifying.

Further, in the toner of the present invention, it is preferable to apply fine silica powder to the surface of the toner particles in order to improve charging stability, developability, fluidity and durability.

The silica fine powder used in the present invention has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more (particularly 50 to 400 m
² / g) gives good results. Toner 100
It is preferable to use 0.01 to 3 parts by weight of the Shiroka derivative per part by weight.

Silica fine powder used in the present invention is, if necessary, hydrophobic, silicone varnish for the purpose of charge control,
Treatment with various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other treating agents such as organosilicon compounds, or in combination with two or more treating agents It is also preferred that it is done.

The toner of the present invention is preferably a magnetic toner satisfying the following conditions, from the viewpoint of developability.

A magnetic toner containing at least a binder resin, a magnetic material and a metal salt or a metal complex, wherein the volume average particle diameter of the magnetic toner is 4.5 to 8 μm (preferably 6 to 8 μm).
m), further comprising 17 to 60% by number of magnetic toner particles having a particle size of 5 μm or less, and 5 to 50% by number of magnetic toner particles having a particle size of 6.35 to 10.08 μm;
2.0% by volume of magnetic toner particles having a particle size of 2.7μm or more
The magnetic toner particles having a particle size distribution satisfying the following formula are contained.

[Wherein N represents the number% of magnetic toner particles having a particle size of 5 μm or less, V represents the volume% of magnetic toner particles having a particle size of 5 μm or less, and k represents a positive number of 4.6 to 6.7. . Here, N indicates a positive number of 17 to 60. If the toner volume average particle size is less than 4.5 μm, the amount of toner on the transfer paper is small and the image density tends to be low in applications having a high image area ratio such as a graphic image. This is considered to be due to the same reason that the density inside the edge portion in the latent image described later decreases. When the volume average particle diameter exceeds 8 μm, the resolution of a digital latent image formed from minute spots of 100 μm or less is not good, and the image quality tends to deteriorate due to durability.

When the number of magnetic toner particles having a particle diameter of 5 μm or less is less than 17% by number, the amount of magnetic toner particles effective for high image quality is small. In particular, as the toner is used by continuing printout, the effective magnetic toner particle component is reduced. Decrease,
The variation in the particle size distribution of the magnetic toner as described in the present invention is worsened, and the image quality tends to be gradually lowered. 60%
When the toner particle diameter exceeds the above range, the magnetic toner particles tend to aggregate with each other, and the toner particles become larger than the original particle diameter, resulting in rough image quality, lower resolution, and a difference in density between the edge portion of the latent image and the inside. And the image tends to be slightly hollow.

5 to 50% by number of toner particles in the range of 6.35 to 10.08 μm
The number is preferably 8 to 40% by number. If the content is more than 50% by number, the image quality is deteriorated, and the development is performed more than necessary (that is, the toner is excessively applied), the reproducibility of fine lines is reduced, and the toner consumption is increased. 5
If it is less than the number%, it becomes difficult to obtain a high image density.

Number% of magnetic toner particles having a particle size of 5 μm or less (N
%) And the volume% (V%) preferably have a relationship of N / V = −0.05N + k, where k is a positive number in the range of 4.6 ≦ k ≦ 6.7. FIG. 10 shows a preferred range in the present invention. Preferably 4.6 ≦ k ≦ 6.2, more preferably 4.6
≦ k ≦ 5.7. As indicated above, 17 ≦ N ≦ 60, preferably 25 ≦ N ≦ 60, more preferably 30 ≦ N ≦ 60.

When k ≦ 4.6, the number of magnetic toner particles having a particle diameter smaller than 5.0 μm is small, and image density, resolution, and sharpness are likely to be inferior. The appropriate presence of fine magnetic toner particles, which was conventionally considered unnecessary, contributes to the closest packing of the toner in development and contributes to the formation of a uniform image without roughness. In particular, by uniformly filling the fine lines and the contours of the image, the sharpness is further enhanced visually. When k <4.6, these properties tend to be inferior due to the lack of the particle size distribution component.

From another aspect, in production, a large amount of fine powder must be cut by classification to satisfy the condition of k <4.6, which is disadvantageous in terms of yield and toner cost.
When k> 6.7, the image density tends to decrease during repeated printout due to the presence of unnecessarily fine powder. Such a phenomenon is considered to be caused by excessive fine magnetic toner particles having a charge more than necessary being charged and adhered to the developing sleeve, thereby impeding normal magnetic toner from being carried on the developing sleeve and charged. Can be

The content of the magnetic toner particles having a particle size of 12.7 μm or more is preferably 2.0% by volume or less, more preferably 1.0% by volume or less, and further preferably 0.5% by volume or less. If it is more than 2.0% by volume, it will hinder the reproduction of fine lines.

Although the particle size distribution of the toner can be measured by various methods, in the present invention, the measurement was performed using a Coulter counter.

As a measuring device, a Coulter Counter TA-II type (manufactured by Coulter) is used, and an interface (manufactured by Nikkaki) which outputs a number distribution and a volume distribution and a CX-1 personal computer (manufactured by Canon) are connected. Prepare an approximately 1% NaCl aqueous solution using primary sodium chloride. As a measuring method, 0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the aqueous electrolytic solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and using the Coulter Counter TA-II, using a 100 μ aperture as an aperture,
The particle size distribution of the particles of 2 to 40 μ is measured on the basis of the number, and the value according to the present invention is determined therefrom.

The image forming method and apparatus of the present invention will be specifically described with reference to FIG.

The surface of the photoconductor 1 is charged to, for example, a negative polarity by the primary charger 2, and a latent image (for example, a digital latent image is formed by image scanning) is formed by exposure, for example, a laser beam 5, and the magnetic blade 11 and the magnet 14 are included therein. Developing sleeve 4
The latent image is developed (for example, reversal development) with a one-component magnetic developer 10 containing a magnetic toner in a developing device 9 provided with a developing device.
In the developing section, between the conductive substrate of the photosensitive drum 1 and the developing sleeve 4, an alternating bias, a pulse bias and / or a DC bias are applied by a bias applying means 12. When the transfer paper P is conveyed and arrives at the transfer section, the transfer unit 3 charges the back surface (the surface opposite to the photosensitive drum side) of the transfer paper P, so that the developed image (toner image) on the surface of the photosensitive drum is transferred. It is electrostatically transferred onto P. Photosensitive drum 1
The transfer sheet P separated from the transfer sheet P is subjected to a fixing process to fix a toner image on the transfer sheet P by the heating / pressing roller fixing device 7.

The magnetic toner remaining on the photosensitive drum after the transfer process is removed by a cleaning device 8 having a cleaning blade. After the cleaning, the photosensitive drum 1 is gradually charged by the erase exposure 6, and the process starting from the charging process by the primary charger 2 is repeated again.

The electrostatic image carrier (photosensitive drum) has a photosensitive layer and a conductive substrate, and moves in the direction of the arrow. The non-magnetic cylindrical developing sleeve 4 as a toner carrier rotates in the developing section so as to advance in the same direction as the surface of the electrostatic image holding member. Inside the non-magnetic cylindrical sleeve 4, a multi-pole permanent magnet (magnet roll) as a magnetic field generating means is arranged so as not to rotate. The magnetic toner 10 in the developing device 9 is applied on a non-magnetic cylindrical surface,
The toner particles are given, for example, a negative triboelectric charge by friction between the surface of the developing sleeve 4 and the toner particles. Furthermore, the magnetic doctor blade 11 made of iron is brought close to the surface of the cylindrical developing sleeve (at an interval of 50 μm to 500 μm).
m), the thickness of the magnetic toner layer is reduced (30 μm to 30 μm) by disposing the multi-pole permanent magnet so as to face one magnetic pole position.
0 μm) and uniformly regulated, and a magnetic toner layer thinner than the gap between the electrostatic image holder 1 and the developing sleeve 4 in the developing section is formed in a non-contact manner. This developing sleeve 4
Is adjusted so that the sleeve surface speed is substantially equal to or close to the speed of the electrostatic image holding surface. The opposed magnetic poles may be formed by using permanent magnets instead of iron as the magnetic doctor blades 11. In the developing section, the developing sleeve 4 and the electrostatic image holder 1
An AC bias or a pulse bias may be applied by the bias means 12 to the surface. This AC bias may be such that f is 200 to 4,000 Hz and Vpp is 500 to 3,000 V.

Upon transfer of the toner particles in the developing portion, the toner particles are transferred to the electrostatic image side by the action of the electrostatic and AC bias or the pulse bias on the electrostatic image holding surface.

Instead of the magnetic doctor blade 11, an elastic blade made of an elastic material such as silicone rubber may be used to control the thickness of the magnetic toner layer by pressing and apply toner on the developing sleeve.

When the image forming apparatus of the present invention is used as a facsimile printer, the light image exposure L is an exposure for printing received data. FIG. 12 is a block diagram showing an example of this case.

The controller 511 controls the image reading unit 510 and the printer 519. The whole controller 511 is controlled by the CPU 517. The read data from the image reading unit is transmitted to the transmission circuit 51.
Sent to the other station through 3. Data received from the partner station is sent to the printer 519 through the receiving circuit 512. Predetermined image data is stored in the image memory. The printer controller 518 controls the printer 519. 514
Is a telephone.

The image received from the line 515 (image information from a remote terminal connected via the line) is demodulated by the receiving circuit 512, and then the CPU 517 performs a decoding process of the image information and is sequentially stored in the image memory 516. You. When at least one page image is stored in the memory 516, the page image is recorded. The CPU 517 reads out one page of image information from the memory 516, and sends out the decoded one page of image information to the printer controller 518. When the printer controller 518 receives the image information of one page from the CPU 518, the printer controller 518 prints the image information of the page.
Control 519.

The CPU 517 is receiving the next page during recording by the printer 519.

 As described above, image reception and recording are performed.

As an electrophotographic apparatus, a plurality of components such as an electrostatic latent image carrier such as the above-described photosensitive drum, a developing device, and a cleaning unit are integrally connected as an apparatus unit, and this unit is used as an apparatus main body. May be configured to be detachable with respect to. For example, a unit is formed by integrally supporting at least one of the charging unit, the developing device, and the cleaning unit together with the photosensitive drum, and the unit is detachably attached to the apparatus main body. Any configuration may be used. At this time, the device unit may be provided with a charging unit and / or a developing device.

Hereinafter, the present invention will be specifically described based on examples.

Synthesis Example 1 200 parts by weight of cumene was placed in a reactor and heated to the reflux temperature. The following mixture was added dropwise over 4 hours under cumene reflux.

Further, the polymerization was completed under cumene reflux (146-156 ° C),
Cumene was removed. The obtained uncrosslinked styrene-based copolymer had a main peak at a molecular weight of 5000, and had a glass transition temperature (Tg) of 60 ° C. 30 parts by weight of the uncrosslinked styrene-based copolymer was dissolved in the following monomer mixture to prepare a monomer mixture.

170 parts by weight of water in which 0.1 part by weight of a partially saponified polyvinyl alcohol was dissolved was added to the monomer mixture to prepare a suspension dispersion. The suspension dispersion was added to a reactor filled with 15 parts by weight of water and purged with nitrogen, and a suspension polymerization reaction was performed at a reaction temperature of 70 to 95 ° C. for 6 hours. After completion of the reaction, the mixture was filtered, dehydrated, and dried, and styrene-acrylic acid n containing styrene-n-butyl acrylate-maleic acid-maleic anhydride copolymer was used.
A resin composition of -butyl-monobutyl maleate copolymer was obtained. The obtained resin composition has a THF insoluble content of 40% by weight,
g is 59 ° C, JIS acid value (A) is 18.4, ratio of total acid value (B) A /
B was 0.90, and the molecular weight distribution of the soluble matter in THF was a peak at a molecular weight of about 5,000 in the GPC chart, and had a shoulder at a molecular weight of about 34,000.

The THF-insoluble content of the resin composition was measured as described below.
About 0.5 g (W ₁ ) of the resin composition was weighed, placed in a cylindrical filter paper (No. 86R: 28 × 100 mm, manufactured by Toyo Roshi Kaisha), subjected to a Soxhlet extractor, and extracted with 200 ml of THF as a solvent for 6 hours. The extraction cycle of THF in a Soxhlet extractor is about 4
Once a minute. After evaporating the THF-soluble component extracted with THF, the solution was dried under reduced pressure at a temperature of 100 ° C., and the weight (W ₂ ) of the THF-soluble component was weighed.

In the present invention, the glass transition point (Tg) of the resin was measured using a differential thermal analyzer (DSC measuring device), DSC-7 (manufactured by PerkinElmer) according to the ASTM D3418-82 method.

Synthesis Example 2 The above components were added dropwise to 200 parts by weight of cumene heated to the reflux temperature over 4 hours. In addition, under cumene reflux (146
156156 ° C.) to complete the solution polymerization and remove cumene. The resulting styrenic copolymer is a GPC chart with a molecular weight of 5,200.
And the Tg was 62 ° C.

30 parts by weight of the styrene copolymer was dissolved in the following monomer mixture to prepare a mixed solution.

In the above mixed solution, partially saponified polyvinyl alcohol
170 parts by weight of water in which 0.1 part by weight was dissolved was added to obtain a suspension dispersion. The suspension dispersion was added to a reactor filled with 15 parts by weight of water and purged with nitrogen, and a suspension polymerization reaction was performed at a reaction temperature of 70 to 95 ° C. for 6 hours. After the completion of the reaction, the resultant was separated by filtration, dehydrated and dried to obtain a resin composition containing a crosslinked styrene-n-butyl acrylate-monobutyl maleate copolymer. The obtained resin composition is 55% by weight insoluble in THF, Tg is 54 ° C., JIS acid value A is 13.0, ratio A / B to total acid B is 0.97, and molecular weight distribution of THF soluble component is GPC chart molecular weight. Peak at about 6000,
He had a shoulder at about 32,000 positions.

Synthesis Example 3 The mixture was added dropwise to the reactor containing 200 parts by weight of xylene and heated to the reflux temperature over 4 hours under reflux of xylene.

Further, the solution polymerization was completed under xylene reflux (138 to 144 ° C.), and xylene was removed. The obtained uncrosslinked styrenic copolymer had a main peak at a molecular weight of 5,500, and had a Tg of 63 ° C.

20 parts by weight of the styrene copolymer was dissolved in the following monomer mixture to prepare a mixed solution.

Polyvinyl alcohol partially saponified in the above mixed solution 0.
170 parts by weight of water in which 1 part by weight was dissolved was added to obtain a suspension dispersion. The suspension dispersion was added to a reactor filled with 15 parts by weight of water and purged with nitrogen, and a suspension polymerization reaction was performed at a reaction temperature of 70 to 95 ° C. for 6 hours. After completion of the reaction, filtration, dehydration and drying were performed to obtain a resin composition containing a styrene-n-butyl acrylate-monobutyl maleate copolymer. Of the obtained resin composition
THF insoluble content is 30% by weight, tg is 57 ° C, JIS acid value A30.5, ratio A / B to total acid value B is 0.81, molecular weight distribution of THF soluble component is about 6200, It had a peak at 36,000.

Comparative Synthesis Example 1 The above material was dropped into 200 parts by weight of cumene heated to the reflux temperature over 4 hours. Furthermore, under cumene reflux (146-1
(56 ° C.) to complete the solution polymerization and remove cumene. The obtained styrene polymer had a molecular weight at the position of the main peak in the GPC chart of 4,000, and a Tg of 67 ° C.

30 parts by weight of the styrene polymer was dissolved in the following monomer mixture to prepare a mixed solution.

In the above mixed solution, partially saponified polyvinyl alcohol
170 parts by weight of water in which 0.1 part by weight was dissolved was added to obtain a suspension dispersion. The suspension dispersion was added to a reactor filled with 15 parts by weight of water and purged with nitrogen, and a suspension polymerization reaction was performed at a reaction temperature of 70 to 95 ° C. for 6 hours. After completion of the reaction, filtration, dehydration and drying were performed to obtain a resin composition of polystyrene and an uncrosslinked styrene-n-butyl acrylate copolymer. The obtained resin composition is THF
Soluble in water and has a molecular weight distribution of about 450
It had peaks at 0 and about 30,000, Tg was 60 ° C, and JIS acid value A was 0.6.

Comparative Synthesis Example 2 170 parts by weight of water obtained by dissolving 0.1 part by weight of a partially saponified polyvinyl alcohol was added to the following monomer mixture to prepare a suspension dispersion.

This suspension dispersion was added to a reactor filled with 15 parts by weight of water and purged with nitrogen, and subjected to a suspension polymerization reaction at a reaction temperature of 70 to 95 ° C. for 6 hours. After completion of the reaction, the mixture was filtered, dehydrated and dried to obtain a crosslinked styrene-n-butyl acrylate-monobutyl maleate copolymer.

In this copolymer, the main peak was at a position of about 17,000 in molecular weight, and there was substantially no peak at a molecular weight of less than 15,000.

The Tg was 60 ° C., the JIS acid value A was 16.6, the ratio A / B to the total acid value B was about 1, and the THF-insoluble content was 30% by weight.

Comparative Synthesis Example 3 200 parts by weight of cumene was charged into a reactor and heated to a reflux temperature. The following monomer mixture was added dropwise thereto over 4 hours.

Further, solution polymerization was carried out for 4 hours under the reflux of cumene, and thereafter, the solvent was removed by ordinary vacuum distillation to obtain a copolymer.

The obtained copolymer had a THF-insoluble content of 5% by weight, peaks at positions of molecular weight of about 17,000 and about 800,000 in GPC chart, Tg of 60 ° C., JIS acid value A of 8.6, and total acid value B. A / B ratio
Was 0.66.

Example 1 After the above materials were mixed well in a blender, they were kneaded in a twin-screw kneading extruder set at 130 ° C. Since the melt index value of the formed kneaded product was lower than the melt index value of the kneaded product prepared without adding the complex [I] -2, a new crosslinked structure was formed.

After cooling the obtained kneaded material and coarsely pulverizing with a cutter mill, pulverizing using a fine pulverizer using a jet stream,
The obtained finely pulverized powder was classified by a fixed wall type air classifier to produce a classified powder. Furthermore, the obtained classified powder is strictly classified and removed simultaneously by a multi-division classifier using a Coanda effect (an elbow jet classifier manufactured by Nittetsu Mining Co., Ltd.) to obtain a magnetic toner having a volume average particle diameter of 10 μm. Obtained.

0.6 parts by weight of hydrophobic colloidal silica fine powder treated with silicone oil was dry-mixed with 100 parts by weight of the toner to obtain a magnetic toner having the hydrophobic colloidal silica fine powder on the surface of the magnetic toner particles.

The results of measuring the viscoelasticity of this magnetic toner at temperatures of 120 ° C. and 200 ° C. are shown in FIGS. 1 and 2, respectively. The dynamic elastic modulus G ′ and the loss elastic modulus G ″ are 2 between 120 ° C. and 200 ° C.
It was from × 10 ^{3 to} 5 × 10 ⁵ dyne / cm ² , and G ′ ₁₂₀ / G ′ ₂₀₀ was 40 or less. Furthermore, almost no time-dependent change at 200 ° C. was observed as shown in FIG. Table 2 shows data on viscoelasticity.

For image output, a small laser beam printer (Canon LBP-8II) was modified and the printer speed was changed to 16 sheets per minute (A4 length).
The fixing property, the offset resistance after printing 5,000 sheets, and the heat fixing roller stain were evaluated.

 The development conditions are shown below.

・ Nearest gap with the developing sleeve of the laminated OPC photosensitive drum (including the fixed magnet): about 300 μm ・ Gap between the magnetic blade and the developing sleeve: about 250 μm ・ Thickness of the magnetic toner layer on the coated developing sleeve: about 130 μm
m ・ Developing bias: AC bias (Vpp1600V, frequency 1800
Hz) and DC bias (-390V) fixability is evaluated under normal temperature and normal humidity environment (temperature 23 ° C, humidity 60%) after the power is turned on after the evaluation machine and the fuser inside it have completely adjusted to the environment. Immediately after uploading, a horizontal line pattern of 200 μm width (line width 200 μm)
m, interval 200 μm), and the first printed image was used for evaluation of fixability. The fixing was performed by setting the surface temperature of the heat fixing roller coated with a fluorine-based resin at 180 ° C. The evaluation of fixability was performed using an image of 5
Reciprocating, rubbing with 100g load, peeling of toner image is evaluated by the reduction rate of reflection density (%). Offset resistance is 30 seconds after continuous printing of 300 sheets of 100μm width horizontal line pattern using a new fixing cleaning pad. Then, evaluation was made based on the degree of back stain on the first sheet immediately after printing was started.

The heat-fixing roller stain was visually inspected for stains on the fixing-fixer heat-fixing roller surface after printing 5,000 continuous (A4 length) character patterns with a dot ratio of 4% using a new fixing cleaning pad.

After the above observation, after printing 300 sheets of 100 μm horizontal line pattern continuously (A4 length), pause for 30 seconds and then resume printing,
The offset resistance was evaluated based on the degree of back stain on the first sheet immediately after the restart.

For evaluation, bond paper having a surface smoothness of 10 [sec] or less was used as transfer paper.

 The evaluation criteria are shown below.

(1) Fixability ○: Good △: Slightly poor, but practically acceptable ×: Impossible (2) Dirt of the heat fixing roller in the fixing unit ○: Not dirty at all ○ △: Dirt to a degree that is hardly noticed △: Dirty but practical (No offset) ×… dirt is conspicuous and impractical (occurs with offset) (3) Offset resistance (back dirt after resting) ○… No dirt ○ ほ と ん ど Almost unknown △… Dirty but practical × × Dirty Table 3 shows the evaluation results.

Examples 2 to 4 A toner was produced in the same manner as in Example 1 except that the resin and the metal complex were mixed as shown in Table 2. Table 1 shows the viscoelasticity data of this toner, and Table 2 shows the evaluation results.

Comparative Examples 1 to 3 Toners were produced in the same manner as in Example 1 except that the resin and the metal complex were mixed as shown in Table 2. Table 1 shows the viscoelasticity data of the toner, and Table 2 shows the evaluation results.

Example 5 After the above materials were mixed well in a blender, they were kneaded in a twin-screw kneading extruder set at 130 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, then pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified by a fixed wall type air classifier to obtain a classified powder. Generated. Further, the obtained classified powder was strictly classified and removed simultaneously by a multi-segmentation classifier using a Coanda effect (an elbow jet classifier manufactured by Nittetsu Mining Co., Ltd.) to remove the volume average particle size by 6.5.
A μm magnetic toner was obtained.

Table 3 shows data obtained by measuring the obtained magnetic toner by using a Coulter Counter TA II having an aperture of 100 μm as described above.

1.0 part by weight of hydrophobic colloidal silica fine powder was dry-mixed with 100 parts by weight of the toner to obtain a magnetic toner having hydrophobic colloidal silica on the surface of magnetic toner particles.

The results of measuring the viscoelasticity of this magnetic toner at 120 ° C. and 200 ° C. are shown in FIGS. 5 and 6, respectively. G 'and G "are
It was 2 × 10 ^{3 to} 5 × 10 ⁵ dyne / cm ² from 120 ° C. to 200 ° C., and G ′ ₁₂₀ / G ′ ₂₀₀ was 40 or less. 200 ° C
The change with time was hardly observed as shown in FIGS. 7 and 8. Data on viscoelasticity is shown in Table-4.

For image output, the scanner part of a small laser beam printer (Canon LBP-8II) has been improved so that latent images with minute spots of up to 50 μm can be created, and the print speed has been increased to 16 sheets per minute (A4 length). Using the remodeled machine, the initial image quality, fixability, offset resistance after printing 5,000 sheets, and heat fixing roller contamination were evaluated in the same manner as in Example 1.

The microdot reproducibility is obtained by observing and evaluating the reproducibility of a checker pattern image having a square of 80 μm and 50 μm as shown in FIG. It is.

Examples 6 to 8 Magnetic toners were prepared in the same manner as in Example 5, except that the resin and the metal complex were mixed as shown in Table-4. Table 4 shows the particle size distribution data of the magnetic toner, Table 4 shows the viscoelasticity data, and Table 5 shows the evaluation results.

Example 9 The magnetic material of Example 5 was reduced to 80 parts by weight to obtain a magnetic toner having a particle size distribution shown in Table 4. This magnetic toner 10
0.8 parts by weight of colloidal silica fine powder was dry-mixed with 0 parts by weight to obtain a magnetic toner. Table 3 shows the viscoelasticity data of the magnetic toner, and Table 5 shows the evaluation results.

Comparative Examples 4 to 6 Developers were prepared in the same manner as in Example 5, except that the resin and the metal complex were mixed as shown in Table-3. Table 4 shows the particle size distribution data of this developer, and Table 3 shows the viscoelasticity data.
Table 5 shows the evaluation results.

[Effects of the Invention] The toner of the present invention has fixing properties, offset resistance, pulverizability,
The present invention achieves the object of the present invention by exhibiting excellent performance in fixing roller contamination, image density, and dot reproducibility.

[Brief description of the drawings]

FIG. 1 is a graph showing the frequency dispersion (0.01 Hz to 1 Hz) of viscoelasticity at 120 ° C. of the toner of Example 1. FIG. 2 is a graph showing frequency dispersion (0.01 Hz to 1 Hz) of viscoelasticity of the toner of Example 1 at 200 ° C. FIGS. 3 and 4 show the toner of Example 1 at 200 ° C., 0.1 Hz and 1 Hz.
4 is a graph showing a change over time in viscoelasticity at Hz. FIG. 5 is a graph showing the frequency dispersion (0.01 Hz to 1 Hz) of the viscoelasticity of the toner of Example 5 at 120 ° C. FIG. 6 is a graph showing the frequency dispersion (0.01 Hz to 1 Hz) of the viscoelasticity of the toner of Example 5 at 200 ° C. 7 and 8 show the toner of Example 5 at 200.degree.
4 is a graph showing a change over time in viscoelasticity at Hz. FIG. 9 shows an image pattern used in the dot reproduction test in the embodiment. FIG. 10 is a graph showing a particle size distribution range of toner particles having a particle size of 5 μm or less in a preferable toner of the present invention. FIG. 11 is a diagram schematically showing a specific example of the image forming method and the image forming apparatus of the present invention. FIG. 12 is a block diagram of a facsimile apparatus using the image forming apparatus of the present invention as a printer.

Continuation of the front page (72) Inventor Koichi Tomiyama 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Tetsuto Kuwashima 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (58) Field surveyed (Int.Cl. ⁶ , DB name) G03G 9/087 G03G 15/08 G03G 15/01

Claims (4)

(57) [Claims] 1. A toner containing at least a binder resin and a metal salt or a metal complex, which is measured at a frequency of 1 × 10 ^-2 to 1 (Hz) at 120 to 200 ° C.
The dynamic elastic modulus G ′ of the toner at _{120 °} to ₂₀₀ ′ is 2 × 10 ³ [dyne /
cm ² ] or more and less than 5 × 10 ⁵ [dyne / cm ² ], and measured at a frequency of 1 × 10 ⁻² to 1 (Hz) at 120 to 200 ° C.
The elastic modulus G ″ of the toner at _{120 °} to ₂₀₀ ″ is 2 × 10 ³ [dyn
e / cm ² ] or more and less than 5 × 10 ⁵ [dyne / cm ² ], and the relationship between the dynamic elastic modulus G ′ _{200 at} 200 ° C. and the frequency f is calculated by the following equation logG ′ ₂₀₀ = a · logf + logb [where, G ′ represents the dynamic elastic modulus of the toner at 200 ° C., f represents the frequency, and a and b represent the constants] The value of a is 0.
A positive number less than 25 and 200 at a frequency of 1 [Hz]
A toner characterized in that the ratio (G ' ₂₀₀ / G' ₁₂₀ ) of the dynamic elastic modulus at 120 ° C. (G ′ ₂₀₀ ) to the dynamic elastic modulus at 120 ° C. (G ′ ₂₀₀ ) is less than 0.25. 2. An electrostatic latent image carrier, a developer carrier for carrying a toner for developing the electrostatic latent image and transporting the toner to a developing area, and a developer accommodating the toner. An image forming apparatus comprising at least a developing device having a chamber, wherein the toner contains at least a binder resin and a metal salt or a metal complex, and has a frequency of 1 × 10 ^-2 to 1 (Hz). 120-200 ℃ measured
The dynamic elastic modulus G ′ of the toner at ₁₂₀ × ₂₀₀ is 2 × 10 ³ [dyn
e / cm ² ] or more and less than 5 × 10 ⁵ [dyne / cm ² ], and measured at a frequency of 1 × 10 ⁻² to 1 (Hz) at 120 to 200 ° C.
The elastic modulus G ″ of the toner at _{120 °} to ₂₀₀ ″ is 2 × 10 ³ [dyn
e / cm ² ] or more and less than 5 × 10 ⁵ [dyne / cm ² ], and the relationship between the dynamic elastic modulus G ′ _{200 at} 200 ° C. and the frequency f is calculated by the following equation logG ′ ₂₀₀ = a · logf + logb [where, G ′ represents the dynamic elastic modulus of the toner at 200 ° C., f represents the frequency, and a and b represent the constants] The value of a is 0.
A positive number less than 25 and 200 at a frequency of 1 [Hz]
Dynamic modulus at ℃ (G _'200) and dynamic elastic modulus of ₁₂₀ ℃ (G' 120) the ratio between _{(G '200 / G' 120} ) is an image forming apparatus and less than 0.25 . 3. An electrostatic latent image carrier and a developing device for developing the electrostatic latent image, the developing device comprising: a developer accommodating chamber for accommodating toner; At least a developer carrier for conveying the toner to the area, wherein the developing device is integrally supported with the electrostatic latent image carrier to form a unit, and is a single unit detachable from the apparatus main body. Wherein the toner contains at least a binder resin and a metal salt or a metal complex, and is measured at a frequency of 1 × 10 ⁻² to 1 (Hz) at 120 to 200 ° C.
The dynamic elastic modulus G ′ of the toner at ₁₂₀ × ₂₀₀ is 2 × 10 ³ [dyn
e / cm ² ] or more and less than 5 × 10 ⁵ [dyne / cm ² ], and measured at a frequency of 1 × 10 ⁻² to 1 (Hz) at 120 to 200 ° C.
The elastic modulus G ″ of the toner at _{120 °} to ₂₀₀ ″ is 2 × 10 ³ [dyn
e / cm ² ] or more and less than 5 × 10 ⁵ [dyne / cm ² ], and the relationship between the dynamic elastic modulus G ′ _{200 at} 200 ° C. and the frequency f is calculated by the following equation logG ′ ₂₀₀ = a · logf + logb [where, G ′ represents the dynamic elastic modulus of the toner at 200 ° C., f represents the frequency, and a and b represent the constants] The value of a is 0.
A positive number less than 25 and 200 at a frequency of 1 [Hz]
Device Yunitsuto the dynamic modulus at ℃ (G _'200) and dynamic elastic modulus of 120 ° C. (G' ratio of _{120) (G '200 / G} ' 120) is equal to or less than 0.25. 4. A facsimile apparatus comprising at least an electrophotographic apparatus and a receiving means for receiving image information from a remote terminal, wherein the electrophotographic apparatus includes an electrostatic latent image carrier and an electrostatic latent image developing device. A developing device, wherein the developing device has a developer accommodating chamber for accommodating toner, and a developer carrying member for carrying the toner and transporting the toner to the developing area, wherein the toner has a binder. It contains at least a resin and a metal salt or metal complex, and is measured at a frequency of 1 × 10 ^-2 to 1 (Hz) at 120 to 200 ° C.
The dynamic elastic modulus G ′ of the toner at ₁₂₀ × ₂₀₀ is 2 × 10 ³ [dyn
e / cm ² ] or more and less than 5 × 10 ⁵ [dyne / cm ² ], and measured at a frequency of 1 × 10 ⁻² to 1 (Hz) at 120 to 200 ° C.
The elastic modulus G ″ of the toner at _{120 °} to ₂₀₀ ″ is 2 × 10 ³ [dyn
e / cm ² ] or more and less than 5 × 10 ⁵ [dyne / cm ² ], and the relationship between the dynamic elastic modulus G ′ _{200 at} 200 ° C. and the frequency f is calculated by the following equation logG ′ ₂₀₀ = a · logf + logb [where, G ′ represents the dynamic elastic modulus of the toner at 200 ° C., f represents the frequency, and a and b represent the constants] The value of a is 0.
A positive number less than 25 and 200 at a frequency of 1 [Hz]
Facsimile apparatus characterized by dynamic elastic modulus (G _'200) and dynamic elastic modulus of 120 ° C. (G' ratio of _{120) (G '200 / G} ' 120) is less than 0.25 at ° C..